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Spectroscopy
Jahn-Teller distortions can be observed using a variety of
spectroscopic techniques.

In UV-VIS absorption spectroscopy, distortion causes
splitting of bands in the spectrum due to a reduction in
symmetry (Oh to D4h).

Consider a hypothetical molecule with octahedral
symmetry showing a single absorption band.

If the molecule were to undergo Jahn-Teller distortion, the
number of bands would increase

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Where the spectrum comes from?

The spectrum of complex compounds comes from the
electronic transition which is limited by rules, one of it is
Laporte selection rule.
The Laporte selection rule says that transitions from
centrosymmetric to centrosymmetric (or noncentrosymmetric to non-centrosymmetric) are forbidden
and this means that a transition from the t2g to eg should
not occur.
However, molecular vibrations mean that a certain
proportion of molecules will lose their centre of symmetry
at any instant and can thus undergo the transition.

Besides that, in the transitions electrons cannot change

their spin state when they undergo d-d transitions.
One of the example is in high spin d5 octahedral
complexes have very pale colours or even colourless such
as in [Mn(OH2)6]2+.

Forbidden transition

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Another unique characteristic of an absorption spectrum

of complex compound is it has a "shoulder" at shorter
wavelength absorption.
For this case, let consider something dierent such as high
spin d4 and we want to put the 4th electron. The fourth
electron can have 2 possibilities, at dx2-y2 or dz2, but does it
really matter where the electron is?

If we consider the 4th electron in dz2, so the ligands on the z

axis feel extra repulsion and moves out a bit that makes
ligands on the x and y axes feel less so can move in a bit.
Therefore, we get a distorted octahedral structure:
tetragonal elongation.

This distortion changes the splitting in octahedral splitting where all

the orbitals with a z component are stabilised and the ones without
are destabilised. The stabilisation energy of this distortion (1 and 2)
are much smaller than o, just a few kJ mol-1.

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If we consider the 4th electron in dx2-y2, so the ligands on

the x and y axes feel extra repulsion and move out a bit
whereas the ligands on the z axes feel less so can move in
a bit.
Then, in this case we have a distorted octahedral structure:
tetragonal compression

In this distortion the orbitals in xy plane are stabilised but the

others are destabilised.

Similar phenomenon can be seen with IR and Raman

vibrational spectroscopy.
The number of vibrational modes for a molecule can be
calculated using the 3n - 6 rule (or 3n - 5 for linear
geometry) rule.
If a molecule exhibits an Oh symmetry point group, it will
have fewer bands than that of a Jahn-Teller distorted
molecule with D4h symmetry.
Thus, one could observe Jahn-Teller eects through either
IR or Raman techniques.
This eect can also be observed in EPR experiments as long
as there is at least one unpaired electron.

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The IrvingWilliams series summarizes the relative stabilities

of complexes formed by M2+ ions, and reects a combination
of electrostatic eects and LFSE.
The general stability sequence of high spin octahedral metal
complexes for the replacement of water by other ligands is:

This trend is essentially independent of the ligand, but, since

formation constants refer to forming complexes from aqua
ions, the ligand concerned has to be able to displace water at
a metal centre.

The color for a coordination complex can be predicted using

the Crystal Field Theory (CFT).
The tendency for coordination complexes to display such a
wide array of colors is merely coincidental; their absorption
energies happen to fall within range of the visible light
spectrum.
Chemists and physicists often study the color of a substance
not to understand its sheer appearance, but because color is
an indicator of a chemical's physical proprieties on the atomic
level.

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The electromagnetic spectrum (EM) spectrum is made up of

photons of dierent wavelengths.
This visible light portion has wavelengths in approximately the
400-700 nanometer range (a nanometer, nm, is 10-9 meters).

Each specic wavelength corresponds to a dierent color, and
when all the wavelengths are present, it appears as white
light.

Color is perceived in two ways:

1. through additive mixing, where dierent colors are made by
combining dierent colors of light,
2. and through subtractive mixing, where dierent wavelengths
of light are taken out so that the light is no longer pure white.
For colors of coordination complexes, subtractive mixing is
considered.
3. If none of the light is absorbed, and all is reected back o,
the object appears white;
4. if all of the light is absorbed, and there is none left to reect
or transmit through, the object appears black.

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The idea behind subtractive mixing is that white light (which

is made from all the colors mixed together) interacts with an
object.
The object absorbs some of the light, and then reects or
transmits (or both, depending on the object) the rest of the
light, which contacts the eye.
The object is perceived as whichever color is not absorbed.

Low Spin, Strong Field (o >P)

High Spin, Weak Field (o <P)

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A photon equal to the energy dierence

o can be absorbed, promoting an
electron to the higher energy level.
As certain wavelengths are absorbed in
this process, subtractive color mixing
occurs and the coordination complex
solution becomes colored.
If the ions have a noble gas conguration,
and have no unpaired electrons, the
solutions appear colorless.

In general, a larger indicates that

higher energy photons are absorbed,
and the solution appears further to
the right on the EM spectrum.

This relationship is described in the
equation =hc/, where h and c are
constants, and is the wavelength of
light absorbed.
Using a color wheel can be useful
for determining what color a
solution will appear based on
what wavelengths it absorbs.
If a complex absorbs a particular
color, it will have the appearance
of whatever color is directly
opposite it on the wheel.

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Example: If a solution with a dissolved octahedral complex

appears yellow to the eye, what wavelength of light does it
absorb? Is this complex expected to be low spin or high
spin?
A solution that looks yellow
absorbs light that is violet, which
is roughly 410 nm from the color
wheel.
Since it absorbs high energy, the
electrons must be raised to a
higher level, and o is high, so the
complex is likely to be low spin.

Example: An octahedral metal complex absorbs light with

wavelength 535 nm. What is the crystal eld splitting o for
the complex? What color is it to the eye?
o=hc/
h is Plancks constant and is 6.6251034 Js and
c is the speed of light and is 2.998108m/s.
1 nm is equal to 1109 meters.
o=

(6.6251034Js)(2.998108m/s)
(535nm)(1m /1109nm)

=3.712 J/molecule

Light that is 535 nm is green, and because green light is

absorbed, the complex appears red

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Example 3: There are two solutions, one orange and one blue.
Both solutions are known to be made up of a cobalt complex;
however, one has chloride ions as ligands, while the other has
ammonia ligands. Which solution is expected to be orange?
S/ It is necessary to know the relative strengths of the ligands
involved. CN > en > NH > H O > F >SCN > Cl
3

it is clear that NH3 is a stronger ligand than Cl, which means

that the complex involving NH3 has a greater , and the
complex will be low spin.
Because of the larger , the electrons absorb higher energy
photons, and the solution will have the appearance of a lower
energy color.
Since orange light is less energetic than blue light, the NH3
containing solution is predicted to be orange.

Drawback in the Crystal Field Theory

The crystal eld theory could explain the formation,
structure, optical and magnetic properties of the
coordination compounds quite satisfactorily.
However, the CFT could not explain the following :
The existence of covalent bonding in some transition
metal complexes.
The order of ligands in the spectrochemical series.
On the basis of the assumption that the ligands are point
charges, the anionic ligands should exert greater crystal
eld splitting eect.

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Drawback in the Crystal Field Theory

The crystal eld theory could explain the formation,
structure, optical and magnetic properties of the
coordination compounds quite satisfactorily.
However, the CFT could not explain the following :
However, most of the anionic ligands are found at the
low-end of the spectrochemical series, i.e., these are
considered weak eld ligands.
The OH- ion although lies below H2O and NH3 in the
spectrochemical series but produces a greater crystal eld
splitting.

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Ligand Field Theory can be considered an extension of

Crystal Field Theory such that all levels of covalent
interactions can be incorporated into the model.
Treatment of the bonding in LFT is generally done using
Molecular Orbital Theory.
Ligand >ield theory considers the effect of different ligand
environments (ligand >ields) on the energies of the dorbitals.
The energies of the d orbitals in different environments
determines the magnetic and electronic spectral properties
of transition metal complexes.
Ligand >ield theory combines an electrostatic model of
metal-ligand interactions (crystal >ield theory) and a
covalent model (molecular orbital theory).

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Crystal-eld Theory provides a simple conceptual model

that can be used to interpret magnetic, spectroscopic, and
thermochemical data by using empirical values of O .
The theory is defective because it treats ligands as point
charges or dipoles and does not take into account the
overlap of ligand and metal-atom orbitals.
Crystal-eld Theory cannot account for the ligand
spectrochemical series.
Ligand-eld Theory, which is an application of molecular
orbital theory that concentrates on the d orbitals of the
central metal atom, provides a more substantial framework
for understanding the origins of O .

The Ligand Field Theory incorporates the best

features of both the pure crystal eld theory and
the molecular-orbital theory, and as such is the
superior tool for dealing with the complexes.

Nearly all the results of the Crystal Field Theory
are also valid in the Ligand Field Theory. However,
the former theory in some ways is the easier to
understand.

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The strategy for describing the molecular orbitals of a dmetal complex follows procedures similar to those
described for bonding in polyatomic molecules:
the valence orbitals on the metal and ligand are used to
form symmetry-adapted linear combinations (SALCs),
and then the relative energies of the molecular orbitals
are estimated by using empirical energy and overlap
considerations.
These relative energies can be veried and positioned
more precisely by comparison with experimental data
(particularly UVvisible absorption and photoelectron
spectroscopy)

For octahedral complexes, ligands can interact with metals in a

sigma fashion, donating electrons directly to metal orbitals, or
in a pi fashion, with ligandmetal orbital interactions occurring
in two regions o to the side.

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Consider an octahedral
complex in which each
ligand (L) has a single
valence orbital directed
towards the central metal
atom (M); each of these
o r b i t a l s h a s l o c a l
symmetry with respect to
the ML axis.

The t2g set (dxy, dyz,

dxz) does not have
any electron density
along the bond axes,
so these orbitals do
not participate in
sigma bonding, but
will be involved with
pi bonding.
Since there is a large
disparity in energy
between the ligand
orbitals and the metal
orbitals, the lower
l y i n g m o l e c u l a r
orbitals in the diagram
are essentially ligand
orbitals.

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The d electrons on the

metal will ll the t2g
( n o n - b o n d i n g ) a n d
e g ( a n t i b o n d i n g )
molecular orbitals.
The split between the
H O M O ( h i g h e s t
occupied molecular
orbital) and LUMO
(lowest unoccupied
m o l e c u l a r o r b i t a l )
corresponds to the Do
splitting in crystal eld
theory.
In crystal eld theory, the electrons in these orbitals are viewed as entirely
on the metal atom or ion, whereas in ligand eld theory the electrons are,
to some extent, on the ligands, too.

For a six-coordinate d n
complex, there are 12 + n
electrons to accommodate.

The six bonding molecular
orbitals accommodate the 12
electrons supplied by the
ligands.

The remaining n electrons are
a c c o m m o d a t e d i n t h e
nonbonding t2g orbitals and
the antibonding eg orbitals.
The types of complexes that are obtained (high-spin or low-spin)
depending on the relative values of O and the pairing energy P .
A good -donor ligand should result in strong metalligand overlap,
hence a more strongly antibonding eg set and consequently a larger
value of O .

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pi interactions can have dramatic eects on the t2g orbitals.

The overlap that may

occur between a ligand p
orbital perpendicular to the
ML axis and a metal dxy
orbital.

The orbitals on the metal which were

not used for sigma bonding (the t2g set:
dxy, dyz, dxz) have the same symmetry
properties as combinations of the p
orbitals on the ligands.
If the energy of the metal and ligand
orbitals are comparable, the pi bonding
orbitals formed will be signicantly
lower in energy that the atomic
orbitals on either the metal or ligand.
Likewise, the antibonding pi orbitals will
be much higher in energy. If the orbitals
are very dierent in energy, only slight
mixing will occur.

Ligands which have pi antibonding

orbitals too high in energy to
interact with the metal orbitals. (
base)
Cl, Br, OH , O2, and even H2O are
examples of donor ligands
The gap between the t2g and eg set
will change, because the t2g set is
involved in bonding, so there is not
a no-bonding t 2g set, but an
antibonding t2g set of orbitals. The
gap, represented as o becomes
the gap between the t2g set of
antibonding orbitals and the eg set
of orbitals. As a result, the size of
o dimishes.

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Ligands such as F or Cl have electrons in orbitals

that are not used for sigma bonding, but have the
correct symmetry to interact to t2g orbitals from the
metal.

The bonding is descrive as ligand-tometal (L M) bonding , with the

electrons from the ligands being
donated to the metal ion. Ligands
participating in such interactions are
called donor ligands.

The combined and

donation from the ligands
g i v e s t h e m e t a l m o r e
negative charge, which may
be resisted by metals on the
basis of their relatively low
electronegativities.

Ligand that has empty orbitals

that are available for occupation.
In Lewis acidbase terminology, a
-acceptor ligand is a acid .
Typically, the -acceptor orbitals
are vacant antibonding orbitals
on the ligand (usually the LUMO),
as in CO and N2, which are higher
in energy than the metal d
orbitals.

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Ligands may have empty pi

antibonding orbitals higher in
e n e r g y a n d w i t h t h e s a m e
symmetry as the t2g orbitals of the
metal. These ligands orbitals
interact with the t2g orbitals of the
metal creating a bonding orbital
which is slightly lower in energy
than the t2g set of the metal, and an
antibonding set of orbitals which
are much greater in energy than
the eg set of the complex. The net
result is that the size of the
splitting, o, increases, since the
energy of the t2g bonding orbitals
drops a bit.

Cr(CO)6 is an example of an octahedral complex that has

ligands that can engage in both sigma and pi interactions
with the metal.
The CO ligand has large lobes on carbon in
both its HOMO (3) and LUMO (1*)
orbitals; it is both an eective donor and
acceptor.
As a acceptor, it has two orthogonal *
orbitals, both of which can accept electron
density from metal orbitals of matching
symmetry.
Strong acceptor ligands have the ability to
increase the magnitude of o by lowering
the energy of the t2g orbitals.

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Cr(CO)6

Formally from Cr, ll the three

t2g orbitals, which are also
stabilized (and bonding) by
virtue of the acceptor
interactions.

These are formally the six donor

pairs from the CO ligands that
are stabilized by interacting with
the metal.

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Metal d electrons occupy the bonding

orbitals, resulting in a larger o and
increased metalligand bonding. Figure (a)

Signicant electronic stabilization can result
from this bonding.
This metal-to-ligand (M L)
bonding is also called backbonding .

In back-bonding, electrons from d orbitals of the metal

(electrons that would be localized on the metal if sigma
interactions exclusively were involved) now occupy orbitals
with contribution from the ligands.

Via this interaction,

the metal transfers
some electron density
back to the ligands.

Ligands that have empty orbitals that can engage the metal in
these interactions are therefore called acceptors.

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Filled ligand p orbitals, or even lled * orbitals, that have

energies compatible with metal valence orbitals, result in
L M bonding and a smaller o for the complex.
Empty higher-energy p or d orbitals on the ligands with
comparable energies relative to the metal valence orbitals
can result in M L bonding and a larger o for the
complex.
Extensive ligand-to-metal bonding usually favors highspin congurations, and metal-to-ligand bonding favors
low-spin congurations, consistent with the eect on o
caused by these interactions.

The overall order of the spectrochemical series may be

interpreted in broad terms as dominated by eects (with a
few important exceptions), and in general the series can be
interpreted as follows:

Small O

Intermediate O

Large O

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